Diazotype photoprinting material

ABSTRACT

This invention describes diazotype photoprinting material containing as a coupling component a compound of the formula:   WHEREIN R1 and R2 are hydrogen, alkyl, phenyl, or taken together form a heterocyclic ring and Y is an alkyl or alkoxy. This photoprinting material gives a dense dye-image having high preservability. It could be developed by both dry and wet development methods.

United States Patent [191 Maruyama et a1.

[451 Feb. 12,1974

1 1 DIAZOTYPE PHOTOPRINTING MATERIAL [75] lnventors: Shoji Maruyama, Sagamihara;

Tadashi Saito, Yokohama; Shigfaki Yoshida, Yokohama; Masaru Shimada, Yokohama, all of Japan Related US. Application Data [63] Continuation-impart of Ser. No. 821,968, May 15,

1969, Pat. NO. 3,699,000.

[30] Foreign Application Priority Data Apr. 22, 1969 Great Britain 20378/69 May 14, 1969 Germany 1924685 May 12, 1969 Netherlands 6907274 [52] US. Cl. 96/91 R, 96/49 [51] Int. Cl G03c l/58 [58] Field of Search 96/91, 49, 75

[56] References Cited UNITED STATES PATENTS 3,255,010 6/1966 Sus et a1 96/91 R 2,298,444 10/1942 Weissberger et al.. 961/91 R 2,150,565 3/1939 Schmidt et a1. 96/91 R 2,516,931 8/1950 Von Glahn et al. 96/91 R 3,139,341 6/1964 Schlesinger 96/91 R 3,493,378 2/1970 Sus 96/91 R 3,343,960 9/1967 Sus 96/91 R FOREIGN PATENTS OR APPLICATIONS 491,095 8/1938 Great Britain 96/91 R 554,921 7/1943 Great Britain 96/91 R OTHER PUBLICATIONS Landau, R.; Faseicules 9 & 17 (Les Copulants)", 1962, pages 3 and 50.

Primary Examiner-Charles L. Bowers, Jr.

[57] ABSTRACT This invention describes diazotype photoprinting material containing as a coupling component a com pound of the formula:

wherein R and R are hydrogen, alkyl, phenyl, or taken together form a heterocyclic ring and Y is an alkyl or alkoxy. This photoprinting material gives a dense dye-image having high preservability. 1t could be developed by both dry and wet development methods.

5 Claims, No Drawings 1 DIAZOTYPE PHOTOPRINTING MATERIAL This application is a continuation-in-part of our copending application Ser. No. 821,968 filed May 15, 1969, now US. Pat. No. 3,699,000.

BACKGROUND OF THE INVENTION A Field of the Invention The present inventionrelates to diazotype photoprinting material containing as a coupling component a compound of the foll owing formula:

CHr-N wherein R and R are hydrogen, alkyl radical of from one to five carbon atoms or phenylradical, or they may be linked together with carbon, oxygen, sulfur or nitrogen atom to form a saturated fiveor six-membered heterocyclic ring, and Y is an alkylor alkoxy radical of from one to four carbon atoms.

B. Description of the Prior Art Though derivatives of 1-hydroxy-(4-hydroxy, alkyl or alkoxy)-naphthalene, which are used as coupling components, produce a good dark blue dye-image when coupled with suitable diazo-compounds, they are objectionable in that their solubility in water is very low and the hydroxyl group in the 1- position is so easily oxidized by the effect of the hydroxyl group, alkylor alkoxy radical (i.e., electron donor group) in the 4- position that the photoprinting material containing such a coupling component is readily contaminated by the oxidized coupling component. Consequently, this type of photoprinting material does not yield a good print when developed and the substrate of the printed material is easily discolored. Further, because of the low solubility of the coupling component, the production of the photoprinting material is difficult.

It is, therefore, an object of the present invention to provide a photoprinting material having good quality and containing an improved coupling component.

SUMMARY OF THE INVENTION The present invention relates to diazotype photoprinting material containing as a coupling component a compound of the following general formula:

wherein R and R are hydrogen, an alkyl radical of from one to five carbon atoms or phenyl radical, or they may be linked together with carbon, oxygen, sulfur or nitrogen atoms to form a saturated or sixmembered heterocyclic ring, and Y is an alkylor alkoxy radical of from one to four carbon atoms.

The coupling component gives a good dark blue dyeimage when coupled with a suitable diazo-compound. It is further characterized as being quite soluble in water and exhibits a high antioxidation property. Consequently, when this coupling component is coated on a photoprinting material it advantageously provides a photoprinting material which gives a dense dye-image OH cm OH Hr- H OCH:

l-hydrox -2-dtmethylamtnomet yl--methoxy- M .P. -96 C.

1-hydroxy-2'morphollnomethyl- -methoxynaphthatene naphthalene OH 011 /cm A Hr-NH-Q H:-N\ K/ l Cm (l) OH; I 0 Calls M.P. Ill-112 C. M.P. Slit-81 C. 1-hydroxy-2-anilinomethyll-hydroxy-tdimethylamino- 4-methoxynaphthalene metbyl+ethoxynaphthalene OH OH our-N H b Ely-NEG K/ (3H3 [HI M.P. 77-78 C. M.P. 155157 C. 1-hydr0xy-2-morpholin0- l-hydroxy-Z-anilinomethylmethyl-*t-methylnaphthalene 4-butylnaphthalene HzN b CgHs M.P. -126 C. 1-hydroxy-2-morphollnomethyl tethoxynaphthaleue OH OH CzHr CHr-N H S CH2-N CaH1 I 4110 CH: M.P. 141-143 C. M.P. 71-72 C. l-hydroxy-Z-thiomo holinomethyll-hydroxy-Z-dipropylamino- 4-butoxynap thalene methyl-4-methylnaphthalene M.P. 138-140 C. M.P. 66-67 C. l-hydroxy-Z-anilinomethyll-hydroxy-Z-piperidinomethyl- I t-e'thylnaphthalene 4-butylnaphthalene vvention may be prepared as follows:

,ture of 50 60C for 1 hour. After cooling, white crystals are separated, and 9.8g of pure 1-hydroxy-2- OH OH M.P. 109-110'C. M.P. 8990 O.

1-hydroxy-2-piperidlnomethyll-hydroxy-Z-dimethylamlno- 4-ethoxynaphthalene methyl-4-n-propoxynaphthalene l 5 O C3H7 M.P. 134-136 0. MP. 91.5-9.25 C.

1-hydroxy-Z-morphollnomethyl- 1-hydroxy-2-pyrro1idinomethyl- 4-iso-propoxynaphthalene 4-iso-propoxynaphthalene As the coupling components of this invention are capable of forming water-soluble salts with inorganic or organic acids, a solubilizer is not required for the preparation of a photosensitive solution.

The coupling components which are used in this in- N,N,N,N -tetramethyldiaminomethane, 7.5g (0.0' mol), are added in the solution of 9.4g (0.06 mol) of l-hydroxy-4-ethoxynaphthalene in 100cc of methyl alcohol and this mixture is heated at a temperadimethylamino-methyl-4-ethoxynapththalene (m.p. 81C) are obtained by recrystallization of said white crystals from methyl alcohol. Yield 80 percent.

In this invention, diazo-compounds having the following general formulae (1), (2) and (3) may be suitably used: 7

/Rl XN2 N\ Y2 (1) wherein X is an acidic radical, Y, and Y, are alkoxy radicals of from one to six carbon atoms, R, is hydrogen or an alkyl radical of from one to six carbon atoms, and R is an alkoxy or alkyl radical of from one to six carbon atoms.

A diazo-compound of the general formula (2) is exemplified bythe salt ofl-diazo-Z, 5-diethoxy-4-(4'- methoxy)-benzoyl-amin0benzene.

Diazo eom pounds (3) have the formula:

. 7 Y1 Ra wherein X is an acidic radical, Y and Y are alkoxy radicals of from oneto six carbon atoms, and R is hydrogen, alkyl,or alkoxy radicals of from one to six carbon atoms. v

A diazo-compound of the general formula (3) is. exemplified by the salt of l-diazo-2,5-dimethoxy-4-(4'- methyl)-thiophenylbenzene.

The coupling components of this invention may react with other diazo-compounds. For example, they react with diazo-compounds (having tertiary nitrogen atom) derived from diazotised p-phenylenediamine to give a dense dye-image. They react with diazo-compounds having alkoxy radicals such as a methoxy, ethoxy or butoxy radical in the para-position of the benzene nucleus having the diazo group to give a stable and dense dye-image.

It is understood that the diazotype photoprinting material of this invention is obtained by coating a photosensitive solution containing the aforesaid coupling component and diazo-compound on a surface of the substrate (e.g., paper) and drying it. The photosensitive solution may contain preferably stabilizers such as inorganic acids e.g., hydrochloric acidor boric acid, or-

'ganic acids, e.g., tartaric acid, citric acid'or 1,3,6-

naphthalene tris ulfonic acid or inorganic salts, e.g., zinc chloride or aluminium sulfate and, if necessary, an organic solubilizer (or developing accelerator) such as urea, thiourea, ethylene-glycol or methylethylglycol.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is further illustrated by the following examples.

EXAMPLE 1 A photosensitive solution was prepared from the following ingredients:

citric acid 4.0g thiourea 4.0g conc H 80 0.5 cc l-hydroxy-2-dimethylamino-methyl-4- methoxynaphthalene 1.5g 1-diazo-2,5-dibutoxy-4-morpholinobenzene chloride 1/2ZnCl20.6g water l00cc A diazotype photoprinting material made of said photosensitive solution, gave a dark royal purple dyeimage by overlaying it on the desired-image-carryingoriginal, exposing it to a luminescent lamp and developing it in ammonia vapor or in an alkaline aqueous solution. The substrate of this printed material did change color after exposure to an indoor light for 30 days.

EXAMPLE 2 A photosensitive solution was prepared from the following ingredients:

tartaric acid 5.1g

boric acid 4.0g

thiourea 4.0g

l-hydroxy-Z-piperidino methyl-4-ethoxynaphthalene 2.0g l-diazo-2,5-dimethoxy-4-morpholinobenzene chloride l/2ZnCl20.6g

water 100cc A photoprinting material made of said photosensitive solution, gave a dense blue dye-image by treating it in i the same manner as that in the Example 1 and the substrate of this printed material did not change color after exposure to an indoor light for 30 days.

EXAMPLE 3 A photosensitive solution was prepared from the following ingredients:

citric acid 5.0g boric; acid 2.0g zinc chloride 1.0g thiourea 4.0g 1-hydroxy-2-morpholino-methyl-4-isopropoxynaphthalene 2.0g 1 diazo-4-morpholino-benzene chloride 1/2ZnCl 0.5g water 100cc A photoprinting material made of said photosensitive solution possessed the properties similar to the product described in Example 1.

EXAMPLE 4 A photosensitive solution was prepared from the following ingredients:

citric acid 4.0g conc H 80 0.5cc thiourea 4.0g l-hydroxy-Z-thiomorpholino-methyl-4- butoxynaphthalene 1.7g l-diazo-2,5-dibutoxy-4-morpholinobenzene chloride l/2ZnCl 0.6g water 100cc A photoprinting material made of said photosensitive solution possessed the properties similar to the product described in Example 1.

EXAMPLE 5 A photosensitive solution was prepared from the following ingredients:

tartaric acid 5.lg boric acid 4.0g thiourea 4.0g l-hydroxy-2-dipropylamino-methyl-4- methylnaphthalene 2.2g l-diazo-2,5-dimethoxy-4-morpholinobenzene chloride 1/2ZnClhd 2-0.6g water 100cc A photoprinting material made of said photosensitive solution possessed the properties similar to the product described in Example 2.

EXAMPLE 6 A photosensitive solution was prepared from the following ingredients:

EXAMPLE 7 A photosensitive solution was prepared from the following ingredients:

citric acid 5.0g

conc HCl l.0cc

zinc chloride 2.0g

thiourea 1.0g

l-hydroxy-2-piperidino-methyl-4-butylnaphthalene l-diazo-2-ethoxy-4-diethyl-aminobenzene chloride l/2ZnCl 1.0g water 100cc A photoprinting material made of said photosensitive solution possessed the properties similar to the product described in Example 2.

What is claimed is:

l. A diazotype photoprinting material comprising a support having a photosensitive coating thereon, said coating comprising (a) as a coupling component, a compound of the formula wherein R and R each represent a hydrogen atom, alkyl radical of from one to five carbon atoms or phenyl radical, or when R and R are taken together with the nitrogen atom, form a fiveor sixmembered saturated heterocyclic ring, said ring consisting essentially of carbon, oxygen, sulfur and nitrogen atoms, and Y is an alk oxy group containing from one to four carbon atoms;

(b) a diazonium compound and (c) an acidic stabilizer.

2. A diazotype photoprinting material as defined in claim 1 wherein said coupling component is l-hydroxy- 2-dimethylamino-methyl-4-methoxy-naphthalene.

3. A diazotype photoprinting material as defined in claim 1 wherein said coupling component is l-hydroxy- 2-piperidinomethyl-4-ethoxynaphthalene.

4. A diazotype photoprinting material as defined in claim 1 wherein said coupling component is l-hydroxy- 2-morpholino'methyl-4-isopropoxynaphthalene.

5. A diazotype photoprinting material as defined in claim 1 wherein said coupling component is l-hydroxy- 2-thiomorpholino-methyl-4-butoxynaphthalene. 

2. A diazotype photoprinting material as defined in claim 1 wherein said coupling component is 1-hydroxy-2-dimethylamino-methyl-4-methoxy-naphthalene.
 3. A diazotype photoprinting material as defined in claim 1 wherein said coupling component is 1-hydroxy-2-piperidinomethyl-4-ethoxynaphthalene.
 4. A diazotype photoprinting material as defined in claim 1 wherein said coupling component is 1-hydroxy-2-morpholino-methyl-4-isopropoxynaphthalene.
 5. A diazotype photoprinting material as defined in claim 1 wherein said coupling component is 1-hydroxy-2-thiomorpholino-methyl-4-butoxynaphthalene. 